CN1151352C - Multiple circuit cryogenic liquefaction of industrial gas - Google Patents

Multiple circuit cryogenic liquefaction of industrial gas Download PDF

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Publication number
CN1151352C
CN1151352C CNB991274725A CN99127472A CN1151352C CN 1151352 C CN1151352 C CN 1151352C CN B991274725 A CNB991274725 A CN B991274725A CN 99127472 A CN99127472 A CN 99127472A CN 1151352 C CN1151352 C CN 1151352C
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component
component refrigrant
fluid
refrigrant fluid
cooled
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CN1261654A (en
Inventor
A
A·阿查亚
B·阿曼
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J·A·韦伯
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V·斯里尼瓦桑
ŵ�ֱȶ�˹��
J·J·诺沃比尔斯基
J·斯默拉雷克
��˹��ŵ��
N·T·尼诺夫
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Praxair Technology Inc
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Praxair Technology Inc
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0257—Construction and layout of liquefaction equipments, e.g. valves, machines
    • F25J1/0262—Details of the cold heat exchange system
    • F25J1/0264—Arrangement of heat exchanger cores in parallel with different functions, e.g. different cooling streams
    • F25J1/0265—Arrangement of heat exchanger cores in parallel with different functions, e.g. different cooling streams comprising cores associated exclusively with the cooling of a refrigerant stream, e.g. for auto-refrigeration or economizer
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0005—Light or noble gases
    • F25J1/0007—Helium
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0005—Light or noble gases
    • F25J1/001—Hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0012—Primary atmospheric gases, e.g. air
    • F25J1/0015—Nitrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0012—Primary atmospheric gases, e.g. air
    • F25J1/0017—Oxygen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0012—Primary atmospheric gases, e.g. air
    • F25J1/002—Argon
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0027—Oxides of carbon, e.g. CO2
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0047—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle
    • F25J1/0052—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0047—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle
    • F25J1/0052—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream
    • F25J1/0057—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream after expansion of the liquid refrigerant stream with extraction of work
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/006—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the refrigerant fluid used
    • F25J1/0097—Others, e.g. F-, Cl-, HF-, HClF-, HCl-hydrocarbons etc. or mixtures thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0211—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using a multi-component refrigerant [MCR] fluid in a closed vapor compression cycle
    • F25J1/0214—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using a multi-component refrigerant [MCR] fluid in a closed vapor compression cycle as a dual level refrigeration cascade with at least one MCR cycle
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/14—Carbon monoxide

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation By Low-Temperature Treatments (AREA)

Abstract

A method for more efficiently cooling and liquefying industrial gas wherein refrigeration for the cooling and liquefaction is generated using first and second defined multicomponent refrigerant fluids in separate refrigeration circuits to cover a wide temperature range from ambient to cryogenic temperature.

Description

The method that is used for refrigerating industry gas
Technical field
The present invention relates generally to the liquefaction of industrial gasses, wherein make gas reduce to low temperature to realize described liquefaction from environment temperature.
Background technology
The liquefaction of industrial gasses is the operations that power consumption is bigger.Usually industrial gasses are liquefied by carrying out indirect heat exchange with cold-producing medium.Can go on well aspect the refrigeration though such system provides in the less temperature range that begins from environment temperature, when need be in than large-temperature range, but efficient be not high when realizing refrigeration from environment temperature to low temperature.By using more than one refrigerating circuit can improve this poor efficiency to obtain necessary cryogenic condensation temperature.Yet in order to realize that this system of required result will need huge power input.
Summary of the invention
Therefore, one of target of the present invention provides a kind of multiloop device, takes this industrial gasses to be reduced to colder temperature, particularly low-temperature liquefaction temperature from environment temperature, and this device operates more much effective than various multiloop systems in the past.
Those skilled in the art will be apparent after reading the content of the disclosure more than and other targets can be achieved by following the present invention:
A kind of method that is used for refrigerating industry gas, it comprises:
(A) compression comprises first multi-component refrigrant fluid of at least a component from fluorocarbon, hydrogen fluorocarbon and fluoro-ether;
(B) first multi-component refrigrant fluid after a cooler cooled compressed and cooled first multi-component refrigrant fluid is expanded to produce refrigeration;
(C) make first multi-component refrigrant fluid after the expansion obtain heating by carrying out indirect heat exchange, to realize the further cooling of described cooled first multi-component refrigrant fluid with cooled first multi-component refrigrant fluid;
(D) compression comprises at least a from the component of fluorocarbon, hydrogen fluorocarbon and fluoro-ether and second multi-component refrigrant fluid of at least a atmospheric gas;
(E) second multi-component refrigrant fluid after a cooler cooled compressed, make first multi-component refrigrant fluid after the expansion obtain heating by carrying out indirect heat exchange, to realize the further cooling of described cooled second multi-component refrigrant fluid with cooled second multi-component refrigrant fluid;
(F) further cooled second multi-component refrigrant fluid is expanded to produce refrigeration;
(G) add second multi-component refrigrant fluid after the thermal expansion to realize the further cooling again of described further cooled second multi-component refrigrant fluid by carrying out indirect heat exchange with further cooled second multi-component refrigrant fluid; With
(H) add the first multiple group sub-refrigerating fluid after the thermal expansion and second multi-component refrigrant fluid cooling off described industrial gasses by carrying out indirect heat exchange with industrial gasses,
The various components of described first and second multi-component refrigrants and concentration thereof make first, second multi-component refrigrant form the changing load multi-component refrigrant.
Another is used for the method for refrigerating industry gas, and it comprises:
(A) compression comprise at least a from fluorocarbon, hydrogen fluorocarbon (hydrofluorocarbon) and fluoro-ether component and first multi-component refrigrant fluid of at least a component from fluorocarbon, hydrogen fluorocarbon, fluoro-ether and atmospheric gas;
(B) first multi-component refrigrant fluid after the cooled compressed and cooled compression first multi-component refrigrant fluid is expanded to produce refrigeration;
(C) by with compression after first multi-component refrigrant fluid carry out indirect heat exchange and make first kind of multi-component refrigrant fluid after the expansion obtain heating, to realize the cooling of first multi-component refrigrant fluid after the described compression;
(D) compression comprises at least a from the component of fluorocarbon, hydrogen fluorocarbon and fluoro-ether and second multi-component refrigrant fluid of at least a atmospheric gas;
(E) by with compression after second multi-component refrigrant fluid carry out indirect heat exchange and make first multi-component refrigrant fluid after the expansion obtain heating, with second multi-component refrigrant fluid after the cooled compressed;
(F) further cooling is also expanded through further cooled second multi-component refrigrant fluid to produce refrigeration through cooled compression second multi-component refrigrant fluid;
(G) by with compression after second multi-component refrigrant fluid carry out indirect heat exchange and add second multi-component refrigrant fluid after the thermal expansion to realize the further cooling of second multi-component refrigrant fluid after the described compression; With
(H) add second multi-component refrigrant fluid after the thermal expansion to cool off described industrial gasses by carrying out indirect heat exchange with industrial gasses.
Term used herein " nontoxic " means the danger that acute or slow poisoning can not take place when handling according to acceptable exposure limit.
Term used herein " nonflammable " means does not have flash-point or the very high-flash of 600K at least.
Term used herein " ozone free consumes " means the possibility with zero ozone depletion, does not promptly have chlorine, bromine or iodine atom.
Term used herein " normal boiling point " means in the i.e. boiling temperature under the 14.696 pounds/in2 (definitely) of 1 standard atmospheric pressure.
Term used herein " indirect heat exchange " means between the various fluids and bring various fluids into heat exchange relationship under the situation without any physics contact or mixing.
Term used herein " changing load cold-producing medium " means the mixture of two or more proportional component, the liquid phase of these components experience between the bubble point of mixture and dew point continuously and the variations in temperature that increases progressively.The bubble point of described mixture is the temperature under setting pressure, and this moment, mixture all was in liquid phase, but as adds heat and then will begin to form vapour phase with this liquid equilibrium.The dew point of mixture is the temperature under setting pressure, and this moment, mixture all was in vapour phase, but as therefrom heat removal will begin to form liquid phase with this vapour phase balance.Therefore, the humidity province of mixture between bubble point and dew point is the zone of liquid phase and vapour phase coexistence balance.In enforcement of the present invention, the temperature difference for the changing load cold-producing medium between bubble point and the dew point be at least 10 ° of K, preferably be at least 20 ° of K, most preferably be at least 50 ° of K.
Term used herein " fluorocarbon " means a kind of in the following compound: tetrafluoromethane (CF 4), hexafluoroethane (C 2F 6), perfluoropropane (C 3F 8), perfluorinated butane (C 4F 10), perflenapent (C 5F 12), perfluoroethylene (C 2F 4), perfluoropropene (C 3F 6), perfluorobuttene (C 4F 8), perfluor amylene (C 5F 10), hexafluoro cyclopropane (ring-C 3F 6) and octafluorocyclobutane (ring-C 4F 8).
Term used herein " hydrogen fluorocarbon " means a kind of in the following compound: fluoroform (CHF 3), pentafluoroethane (C 2HF 5), HFC-134a (C 2H 2F 4), heptafluoro-propane (C 3HF 7), HFC-236fa (C 3H 2F 6), pentafluoropropane (C 3H 3F 5), tetrafluoropropane (C 3H 4F 4), nine fluorine butane (C 4HF 9), octafluorobutane (C 4H 2F 8), 11 amyl fluoride (C 5HF 11), fluomethane (CH 3F), difluoromethane (CH 2F 2), fluoroethane (C 2H 5F), Difluoroethane (C 2H 4F 2), HFC-143a (C 2H 3F 3), difluoroethylene (C 2H 2F 2), trifluoro-ethylene (C 2HF 3), fluorinated ethylene (C 2H 3F), five fluorine propylene (C 3HF 5), tetrafluoeopropene (C 3H 2F 4), trifluoro propene (C 3H 3F 3), difluoro propylene (C 3H 4F 2), seven fluorine butylene (C 4HF 7), hexafluoro butylene (C 4H 2F 6) and nonafluoropentene (C 5HF 9).
Term used herein " fluoro-ether " means a kind of in the following compound: trifluoromethoxy-perfluoromethane (CF 3-O-CF 3), difluoro-methoxy-perfluoromethane (CHF 2-O-CF 3), a fluorine methoxy-2-perfluoro methane (CH 2F-O-CF 3), difluoro-methoxy-difluoromethane (CHF 2-O-CHF 2), difluoro-methoxy-hexafluoroethane (CHF 2-O-C 2F 5), difluoro-methoxy-1,2,2,2-HFC-134a (CHF 2-O-C 2HF 4), difluoro-methoxy-1,1,2,2-HFC-134a (CHF 2-O-C 2HF 4), perfluor ethyoxyl-a fluoromethane (C 2F 5-O-CH 2F), perfluor methoxyl group-1,1,2-HFC-143a (CF 3-O-C 2H 2F 3), perfluor methoxyl group-1,2,2-HFC-143a (CF 3O-C 2H 2F 3), the ring-1,1,2,2-tetrafluoro propyl ether (ring-C 3H 2F 4-O-), the ring-1,1,3,3-tetrafluoro propyl ether (ring-C 3H 2F 4-O-), perfluor methoxyl group-1,1,2,2-HFC-134a (CF 3-O-C 2HF 4), the ring-1,1,2,3,3-five fluoropropyl ether (ring-C 3H 5-O-), perfluor methoxy-2-perfluoro acetone (CF 3-O-CF 2-O-CF 3), perfluor methoxy-2-perfluoro ethane (CF 3-O-C 2F 5), perfluor methoxyl group-1,2,2,2-HFC-134a (CF 3-O-C 2HF 4), perfluor methoxyl group-2,2,2-HFC-143a (CF 3-O-C 2H 2F 3), ring-perfluor methoxy-2-perfluoro acetone (ring-CF 2-O-CF 2-O-CF 2-) and ring-perfluoro propyl ether (ring-C 3F 6-O).
Term used herein " atmospheric gas " means a kind of in the following gas: nitrogen (N 2), argon (Ar), krypton (Kr), xenon (Xe), neon (Ne), carbon dioxide (CO 2), oxygen (O 2) and helium (He).
The possibility that term used herein " low-ozone consumes " means ozone-depleting (is defined by the big club of Montreal Protocol, wherein dichlorofluoromethane (CCl less than 0.15 2F 2) the ozone-depleting possibility be 1.0).
Term used herein " expansion " means decompression.
Term used herein " turbine expansion " and " turbo-expander " mean the high-pressure fluid turbine of flowing through respectively and take this to produce the method and apparatus of refrigeration with the pressure and temperature that reduces fluid.
The fluid mixture that term used herein " industrial gasses " means nitrogen, oxygen, argon gas, hydrogen, helium, carbon dioxide, carbon monoxide, methane and contains two or more above-mentioned gas.
Term used herein " low temperature " means the temperature that is not higher than 150 ° of K.
Term used herein " refrigeration " means the ability of heat from the cryogenic system to the ambient atmosphere of repelling.
Description of drawings
Fig. 1 is the schematic flow diagram of a preferred embodiment of multiloop industrial gasses liquefaction system of the present invention, wherein makes industrial gasses obtain cooling by carrying out indirect heat exchange with two kinds of cold-producing mediums that mix.
Fig. 2 is the schematic flow diagram of another preferred embodiment of multiloop industrial gasses liquefaction system of the present invention, and it also adopts the turbine expansion of phase separation and mix refrigerant.
The specific embodiment
Generally speaking, the present invention includes the mix refrigerant of at least two kinds of qualifications of use so that refrigeration to be provided effectively in very big temperature range.
Multi-component refrigrant fluid can provide the refrigeration of variable in required temperature range.For the various industrial gasses that liquefy effectively, the multi-component refrigrant fluid that the present invention limits can provide refrigeration efficiently in quite wide temperature range.The useful in the embodiment of this invention higher multi-component refrigrant fluid of first or temperature comprises at least a component and at least a component from fluorocarbon, hydrogen fluorocarbon, fluoro-ether and atmospheric gas from fluorocarbon, hydrogen fluorocarbon and fluoro-ether.Useful in the embodiment of this invention preferred first multi-component refrigrant fluid comprises at least a component and at least a atmospheric gas from fluorocarbon, hydrogen fluorocarbon and fluoro-ether.Useful in the embodiment of this invention another kind of preferred first multi-component refrigrant fluid comprises at least a fluoro-ether and at least a component from fluorocarbon, hydrogen fluorocarbon, fluoro-ether and atmospheric gas.That the useful in the embodiment of this invention lower multi-component refrigrant fluid of second or temperature comprises is at least a, preferred at least two kinds of component and at least a atmospheric gases from fluorocarbon, hydrogen fluorocarbon and fluoro-ether.Useful in the embodiment of this invention preferred second multi-component refrigrant fluid comprises at least two kinds of component and at least two kinds of atmospheric gases from fluorocarbon, hydrogen fluorocarbon and fluoro-ether.Useful in the embodiment of this invention another kind of preferred second multi-component refrigrant fluid comprises at least a fluoro-ether and at least a atmospheric gas.
Each of the first and second multiple group sub-refrigerating agent compositions is except efficient, and each that its another one benefit is these mixtures all is nontoxic, nonflammable and ozone free consumes.In a preferred embodiment of the invention, the normal boiling point of each other component differs at least 5 ° of K in its normal boiling point of each of two or more component of each first and second multiple group sub-refrigerating agent composition and this refrigerant mixture.This provides refrigeration to improve validity for (comprise low temperature) in the temperature range of wide area.In another preferred embodiment of the present invention, the normal boiling point of the maximum boiling point component of each of the first and second multiple group sub-refrigerating agent compositions is than the high at least 50 ° of K of normal boiling point of the minimum boiling point component of this multiple group sub-refrigerating agent composition.
The present invention further describes with reference to the accompanying drawings.Referring now to Fig. 1, first multi-component refrigrant fluid 19 is compressed into absolute pressure by the compressor 30 of flowing through and is generally 100-600 pound/inch 2(psia).Its heat of compression in aftercooler 31 of first multi-component refrigrant fluid after being compressed in the pipeline 20 be cooled (wherein preferably by partial condensation), the multi-component refrigrant fluid of winning 21 heat exchanger 130 of flowing through, further cooled off therein, and preferably be condensed fully.Institute's multi-component refrigrant liquid 22 of winning is through valve 32 throttlings, be expanded to therein pressure generally in the scope of 15-50psia to produce refrigeration.This fluid provides refrigeration through the pressure expansion of valve 32 by joule-Thomsons (Joule-Thomson) effect, promptly owing to pressure reduces the temperature that has reduced fluid with constant enthalpy.The temperature of first multi-component refrigrant fluid 23 after expanding usually will be in the scope of 200-250 ° of K.First multi-component refrigrant fluid expands through valve 32 also can cause this fluid evaporator of a part usually.
Then, first multi-component refrigrant fluid that has refrigeration in 23 at stream is heated and evaporation fully therein by heat exchanger 130, thereby is used for first multi-component refrigrant fluid 21 after the cooled compressed by indirect heat exchange.Usually first multi-component refrigrant fluid after the gained in 280-320 ° of K scope heats with temperature in the vapor stream 19 is circulated to compressor 30, begins the kind of refrigeration cycle of higher temperature again.
Second multi-component refrigrant fluid 8 is compressed into pressure through compressor 33 and is generally 100-600psia.Second multi-component refrigrant fluid 9 its heat of compression in aftercooler 34 after the compression is cooled.From second multi-component refrigrant fluid 1 of aftercooler 34 by heat exchanger 130, therein by with the expansion of above-mentioned heating after first multi-component refrigrant fluid carry out indirect heat exchange and obtain cooling.Cooled compression second multi-component refrigrant fluid 3 of gained (can partly be condensed) is further cooled off through flowing through heat exchanger 150, and preferably all is condensed.Gained second multi-component refrigrant fluid 4 is expanded to pressure therein and is generally the scope of 15-100psia to produce refrigeration by joule-Thomsons (Joule-Thomson) effect through valve 35 throttlings then.The temperature of second multi-component refrigrant fluid 5 after expanding usually will be in the scope of 80-120 ° of K.Second multi-component refrigrant fluid expands through valve 35 and also causes this fluid evaporator of a part usually.
Then, second multi-component refrigrant fluid 5 with refrigeration is by heat exchanger 150, obtain heating by carrying out indirect heat exchange therein, and obtain heating to realize its further cooling by carrying out indirect heat exchange therein with cooled compression second multi-component refrigrant fluid with industrial gasses cooling, preferred liquefaction.Gained second multi-component refrigrant fluid in stream 6 from heat exchanger 150 heat exchanger 130 of flowing through, carry out indirect heat exchange by compression second multi-component refrigrant fluid therein, also carry out indirect heat exchange and obtain heating simultaneously with the industrial gasses that cool off with cooling.Usually second multi-component refrigrant fluid after the gained in 280-320 ° of K scope heats with temperature in the vapor stream 8 is recycled to compressor 33, begins the kind of refrigeration cycle of lower temperature again.
Make the industrial gasses of stream in 10, through heat exchanger 130, carry out indirect heat exchange by second multi-component refrigrant fluid therein and obtain cooling with first multi-component refrigrant fluid of heating and heating as nitrogen or Oxygen Flow.Make the gained industrial gasses of stream in 111 from heat exchanger 130 heat exchanger 150 of flowing through then, therein by with the expansion of heating after second multi-component refrigrant fluid carry out indirect heat exchange and obtain cooling (preferably obtain liquefaction), to obtain the industrial gasses 12 after the cooling (preferred liquefaction).Though not shown, be understood that liquid gas 12 can be under the high pressure.Therefore, can expand and phase separation makes the liquid of low pressure can be sent to storage at or uses point to it thereafter, wherein can heat again and reconfigure low-pressure gas at fire end place and feed gas 10 by heat exchanger 150 and 130.As in the art the institute well-known, this low-pressure gas carries out compression to a certain degree so that it is joined in the feed gas 10 with needs.
It will be recognized by those skilled in the art, can adopt than the more loop of two refrigerating circuits shown in the accompanying drawing and implement the present invention.For example, can adopt the system of three or three above refrigerating circuits to implement the present invention.In these situations, the first and second multi-component refrigrant loops of the present invention can be two high-temperature circuit, two low-temperature circuits or two medium temperature loops.
In Fig. 1, adopted single core brass aluminium heater 100 with two parts 130 and 150.High temperature or higher temperature part 130 have 5 passages, and low temperature or lower temperature part 150 have 3 passages.First multi-component refrigrant fluid also plays a part direct refrigerating industry gas except first multi-component refrigrant fluid after cooling and the compression that the high-temperature part 130 of single core heat exchanger 100 is connected and second multi-component refrigrant fluid after compressing after the expansion of heating.
Fig. 2 has illustrated that the present invention adopts 5 heat exchangers, also comprise simultaneously by with the expansion of heating after first multi-component refrigrant fluid carry out another embodiment of indirect heat exchange refrigerating industry gas.It is 45,46,47,48 and No. 49 that these 5 heat exchangers are compiled.In being shown in the embodiment of Fig. 2, industrial gasses at first cool off being lower than under the maximum temperature temperature of heat exchanger, promptly pass through to flow 23 in heat exchanger 46, form stream 24, pass through to flow 5 simultaneously, form stream 107.Second multi-component refrigrant fluid that also has by heat exchanger 46 flows 2, therefrom forms stream 3.The numeral that this embodiment is represented each fluid stream and other equipment is digital identical with the common unit of the embodiment shown in Fig. 1, will no longer describe in detail below.
The embodiment of the present invention that is shown among Fig. 2 has adopted the throttling of second multi-component refrigrant fluid that cools off after expansion of liquids replacement or the additional compression with the generation refrigeration.Referring now to Fig. 2, further cooled second multi-component refrigrant fluid 4 is a kind of two phase flows, is admitted in the phase separator 50.To carry out throttling to produce refrigeration through valve 52 from the steam 51 of phase separator 50 by joule-Thomsons (Joule-Thomson) effect.To carry out turbine expansion to produce refrigeration through liquid turbine machine 54 from the liquid 53 of phase separator 50.Make the stream 55 and 56 of two kinds of gained be combined to form second multi-component refrigrant fluid 57 of expansion with refrigeration, be heated cooling, and industrial gasses cool off (preferred liquefaction) to be similar to above-mentioned mode with second multi-component refrigrant fluid after the realization compression.
In a preferred embodiment, first multi-component refrigrant fluid only is made up of fluorocarbon.In another preferred embodiment, first multi-component refrigrant fluid only is made up of fluorocarbon and hydrogen fluorocarbon.In another preferred embodiment, first multi-component refrigrant fluid only is made up of fluorocarbon and atmospheric gas.In another preferred embodiment, first multi-component refrigrant fluid only is made up of fluorocarbon, hydrogen fluorocarbon and fluoro-ether.In another preferred embodiment, first multi-component refrigrant fluid only is made up of fluorocarbon, fluoro-ether and atmospheric gas.
Can contain other components though be used for first multi-component refrigrant fluid of the invention process, as hydrogen chlorine fluorocarbon (hydrochlorofluorocarbon) and/or hydrocarbon, the not hydrogeneous chlorine fluorocarbon of preferred first multi-component refrigrant fluid.In another preferred embodiment of the present invention, first multi-component refrigrant fluid is hydrocarbonaceous not, the neither hydrogeneous chlorine fluorocarbon of first multi-component refrigrant fluid most preferably, hydrocarbonaceous not again.Most preferably first multi-component refrigrant fluid is nontoxic, nonflammable and ozone free consumes, and most preferably each component of first multi-component refrigrant fluid is fluorocarbon, hydrogen fluorocarbon, fluoro-ether or atmospheric gas.
In a preferred embodiment, second multi-component refrigrant fluid only is made up of fluorocarbon and atmospheric gas.In another preferred embodiment, second multi-component refrigrant fluid only is made up of fluorocarbon, fluoro-ether and atmospheric gas.
Can contain other components though be used for second multi-component refrigrant fluid of the invention process, as hydrogen chlorine fluorocarbon and/or hydrocarbon, the not hydrogeneous chlorine fluorocarbon of preferred second multi-component refrigrant fluid.In another preferred embodiment of the present invention, second multi-component refrigrant fluid is hydrocarbonaceous not, the neither hydrogeneous chlorine fluorocarbon of second multi-component refrigrant fluid most preferably, hydrocarbonaceous not again.Most preferably second multi-component refrigrant fluid is nontoxic, nonflammable and ozone free consumes, and most preferably each component of second multi-component refrigrant fluid is fluorocarbon, hydrogen fluorocarbon, fluoro-ether or atmospheric gas.
The present invention is specially adapted to obtain efficiently low temperature from environment temperature.Table 1-4 has enumerated the preferred embodiment that can be used for the first multi-component refrigrant fluid mixture in the invention process.The concentration range of being given among the table 1-4 is a mole percent.
Table 1
Component concentration ranges
C 5F 12 5-45
C 4F 10 0-25
C 3F 8 10-80
C 2F 6 0-40
CF 4 0-25
Table 2
Component concentration ranges
C 5F 12 5-45
C 3H 3F 5 0-25
C 3F 8 10-80
CHF 3 0-40
CF 4 0-25
Table 3
Component concentration ranges
CHF 2-O-C 2HF 4 5-45
C 4F 10 0-25
CF 3-O-CHF 2 0-20
CF 3-O-CF 3 10-80
C 2F 6 0-40
CF 4 0-25
Table 4
Component concentration ranges
C 3H 3F 5 5-45
C 3H 2F 6 0-25
CF 3-O-CHF 2 10-80
CHF 3 0-40
CF 4 0-25
Table 5-10 has enumerated the preferred embodiment that can be used for the second multi-component refrigrant fluid mixture in the invention process.The concentration range of being given among the table 5-10 is a mole percent.
Table 5
Component concentration ranges
C 5F 12 0-25
C 4F 10 0-15
C 3F 8 0-40
C 2F 6 0-30
CF 4 10-50
Ar 0-40
N 2 0-80
Table 6
Component concentration ranges
C 5F 12 0-25
C 4F 10 0-15
C 3F 8 0-40
CHF 3 0-30
CF 4 10-50
Ar 0-40
N 2 10-80
Table 7
Component concentration ranges
CHF 2-O-C 2HF 4 0-25
C 4F 10 0-15
CF 3-O-CHF 2 0-40
CF 3-O-CF 3 0-20
C 2F 6 0-30
CF 4 10-50
Ar 0-40
N 2 10-80
Table 8
Component concentration ranges
C 3H 3F 5 0-25
C 3H 2F 6 0-15
CF 3-O-CHF 2 0-40
CHF 3 0-50
CF 4 10-50
Ar 0-40
N 2 10-80
Table 9
Component concentration ranges
C 3H 3F 5 0-25
C 3H 2F 6 0-15
C 2H 2F 4 0-20
C 2HF 5 0-20
C 2F 6 0-30
CF 4 10-50
Ar 0-40
N 2 10-80
Ne 0-10
He 1-10
Table 10
Component concentration ranges
C 3H 3F 5 0-25
C 3H 2F 6 0-15
CF 3-O-CHF 2 0-40
CHF 3 0-30
CF 4 10-50
Ar 0-40
N 2 10-80
Ne 0-10
He 1-10
The present invention is specially adapted in wide temperature range, especially to comprise in the scope of low temperature provides refrigeration.In a preferred embodiment of the invention, the normal boiling point of the normal boiling point of each of two or more component of one of them or both of the first and second multiple group sub-refrigerating agent compositions and each other component in this refrigerant mixture differs at least 5 ° of K, more preferably at least 10 ° of K, at least 20 ° of K most preferably.Do like this and improved the validity that refrigeration is provided in the scope that in wide temperature range, is particularly comprising low temperature.In a particularly preferred embodiment according to the invention, the normal boiling point of the maximum boiling point component of first and/or second multi-component refrigrant fluid is than at least 50 ° of K of normal boiling point height of the minimum boiling point component of this multi-component refrigrant fluid, preferably at least 100 ° of K, at least 200 ° of K most preferably.
Form the various components can be used for first and second multi-component refrigrant fluids in the invention process and concentration thereof and make and can form a kind of changing load multi-component refrigrant fluid, and the preferred characteristic that in the whole temperature range of the inventive method, keeps this changing load.Do having significantly improved efficient like this, adopt this method can in so wide temperature range, produce and utilize this refrigeration.Defined various preferred ingredient also has a benefit to be, they can be used to form fluid mixture nontoxic, nonflammable and low or that ozone free consumes.Do like this to provide and be better than the other various advantages of cold-producing medium that routine is generally poisonous, inflammable and/or consumes ozone.
A kind of preferred changing load multi-component refrigrant fluid (nontoxic, nonflammable and ozone free consumption) that can be used as first in the invention process and/or second multi-component refrigrant fluid comprises two or more following component: C 5F 12, CHF 2-O-C 2HF 4, C 4HF 9, C 3H 3F 5, C 2F 5-O-CH 2F, C 3H 2F 6, CHF 2-O-CHF 2, C 4F 10, CF 3-O-C 2H 2F 3, C 3HF 7, CH 2F-O-CF 3, C 2H 2F 4, CHF 2-O-CF 3, C 3F 8, C 2HF 5, CF 3-O-CF 3, C 2F 6, CHF 3, CF 4, O 2, Ar, N 2, Ne and He.
Though the present invention describes in detail with reference to some preferred embodiment, it will be recognized by those skilled in the art in the spirit of claims and category to also have other embodiments of the present invention.For example, the present invention can be used to cooling or cooling and two or more industrial gas that liquefies, and is not only the single industrial gas shown in the accompanying drawing.

Claims (6)

1. method that is used for refrigerating industry gas, it comprises:
(A) compression comprises first multi-component refrigrant fluid of at least a component from fluorocarbon, hydrogen fluorocarbon and fluoro-ether;
(B) first multi-component refrigrant fluid after a cooler cooled compressed and cooled first multi-component refrigrant fluid is expanded to produce refrigeration;
(C) make first multi-component refrigrant fluid after the expansion obtain heating by carrying out indirect heat exchange, to realize the further cooling of described cooled first multi-component refrigrant fluid with cooled first multi-component refrigrant fluid;
(D) compression comprises at least a from the component of fluorocarbon, hydrogen fluorocarbon and fluoro-ether and second multi-component refrigrant fluid of at least a atmospheric gas;
(E) second multi-component refrigrant fluid after a cooler cooled compressed, make first multi-component refrigrant fluid after the expansion obtain heating by carrying out indirect heat exchange, to realize the further cooling of described cooled second multi-component refrigrant fluid with cooled second multi-component refrigrant fluid;
(F) further cooled second multi-component refrigrant fluid is expanded to produce refrigeration;
(G) add second multi-component refrigrant fluid after the thermal expansion to realize the further cooling again of described further cooled second multi-component refrigrant fluid by carrying out indirect heat exchange with further cooled second multi-component refrigrant fluid; With
(H) add the first multiple group sub-refrigerating fluid after the thermal expansion and second multi-component refrigrant fluid cooling off described industrial gasses by carrying out indirect heat exchange with industrial gasses,
The various components of described first and second multi-component refrigrants and concentration thereof make first, second multi-component refrigrant form the changing load multi-component refrigrant.
2. the process of claim 1 wherein that cooled industrial gasses are liquid.
3. the process of claim 1 wherein that the further expansion of cooled second multi-component refrigrant fluid is that joule-Thomsons expands.
4. the process of claim 1 wherein that further the small part that is expanded to of cooled second multi-component refrigrant fluid is a turbine expansion.
5. the process of claim 1 wherein that second multi-component refrigrant fluid comprises at least two kinds of component and at least two kinds of atmospheric gases from fluorocarbon, hydrogen fluorocarbon and fluoro-ether.
6. the process of claim 1 wherein that at least a first and second multi-component refrigrant fluids comprise at least two kinds of following component: C 5F 12, CHF 2-O-C 2HF 4, C 4HF 9, C 3H 3F 5, C 2F 5-O-CH 2F, C 3H 2F 6, CHF 2-O-CHF 2, C 4F 10, CF 3-O-C 2H 2F 3, C 3HF 7, CH 2F-O-CF 3, C 2H 2F 4, CHF 2-O-CF 3, C 3F 8, C 2HF 5, CF 3-O-CF 3, C 2F 6, CHF 3, CF 4, Ar, N 2, Ne and He.
CNB991274725A 1998-12-30 1999-12-28 Multiple circuit cryogenic liquefaction of industrial gas Expired - Fee Related CN1151352C (en)

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